Process for hydrogenating organic substances



SFE'ILKER AND EARL ZERBE, OF DUISBURG-MEIDERICH, GERMANY, ASSIGNO'RS T 3 GESELLSCHAFT FUR TEERVERVZERTUNG, M. 13. IL, OF DUISBURG-MEIDERICH,

PROCESS FOR HYDROGENA'IING ORGANIC SUBSTANCES 33o Drawing. application.- filed September 16, 1927, Serial No. 220,057, and in Germany September 23, 1926.

it is known that hydrogen iodide parts bitrarily prepared mixture of halogen comwith hydrogen at elevated temperatures, and pounds, use can also be made, with great thereby acts as a powerful reducing agent. advantage, of crude mixtures, such as occur Phosphorous is frequently added in this in nature, or in the form of mother liquors method of reduction, in order to reconvert in the potash industry, or as intermediate 55 the liberated iodine into-hydrogen iodide in products in the production of bromine and the presence of water and thus bring it into iodine from algae and sea weeds. action again. The reaction proceeds so rapidly at tem- We have found that under high pressure, peratures between 200 and 500 C. and over, 1g suitably high temperature and in the preswith a hydrogen pressure of 2OO or more ence of even very small quantities of iodine, atmospheres, that, the reaction temperature hydrogen itself enters with surprising rcadiremaining constant, the pressure in the presness into additive combination with organic sure vessel decreases to a noticeable extent. substances, such as coals and their distilla- A particularly noteworthy point, and one 15 tion products and especially hydrocarbons, of technically economic value is that only and also with the other constituents of tars, small quantities of iodine or halogen or their including, for example, pitch, and thereby compounds are needed to reduce very large extensively hydrogenates and more or less amounts of the substance under treatment; splits up said substances. and that in the method according to this in 2Q Instead of, or as well as iodine, certain vention, impurities, such as sulphur or other 7 compounds of iodine,-e. g. hydrogen iocontact poisons, in the substances to be redide or ferrous iodide,which readily part duced, or in the hydrogen, have no injurious with iodine or hydrogen iodide at the temeffect. I

perature of the reaction, can be used. The inventioniis illustrated by the follow- 25 iodine compounds which do not by theming examples. selves dissociate or only do so with difficulty (1). 10 kilos of drained crude naphthaat the reaction temperature and prevailing lene are treated with about 1 gram or less,

working conditions can be used in conjuncof iodine in an iron pressure vessel, fitted tion with suitable compounds which react with stirrers and adapted to stand a pres- 30 with the said iodine compounds under the sure of at least 200 atmospheres. Hydrospecified conditions and either liberate iogen, which need not be pure, is then admitdine itself or form iodine compounds, which ted under pressure of 50l00 atmospheres, are readily dissociatd. Such compounds and the whole is heated to 3()O500 U. The comprise more particularly metallic salts, pressure, which increased at the outset 0W- 35 such as iron alum, ferric chloride, copper ing to the rising temperature, very soon be- 35 sulphate or other metallic salts which libergins to sink at about 580 C. (constant temate iodine or hydrogen iodide even from pcrature), an indication that hydrogen has alkali iodides or alkaline earth iodides and been absorbed. If the quantity of hydroallow them to come into intensive action. gen employed has been insufiicient to comas We have further found that the other plete the reaction, a furthe' amount of hy- 9c halogens and halogen compounds also act in drogen-can be forced in after cooling, and the same manner as, iodine, though to a the reaction carried further, or to complesi'naller extent and at higher temperatures. tion, by rencwedheating.

A remarkably chcient action is obtained According to the temperature employed, s5 more particularly when several halogtns or the product is a mixture of low-boiling bentheir compounds are employed in w-mjunczol hydrocarbons and tetralin, which may tion. in this case also, an addition of suit also contain decalin and other hydrocarbons able metallic salts facilitates the dissociaaccording to the method of conducting the tions of l halogen compounds and is exoperation. traordinarily clllt'l 'i -m'. In place of the ary In this manner and under suitable work- 10a hydrogenation products ing conditions. there can be obtained from the 10 kilos of crude naphthalene up to 8 kilos and more of liquid hydrocarbons hoiling up to 200 C. lene, which can be separated by distillation, can be used again. Impurities, such as phenols, bases, thionaphthene and the like, in the naphthalene, give no more trouble than any impurities present in the hydrogen, and are themselves more or less completely reduced.

(2). 10 kilos of ordinary coal-tar pitch are treated with iodine and the requisite quantity of hydrogen, in the same manner as in Example 1.. According to the degree of temperature and pressure employed and the duration of the reaction, there are formed, in addition to an abundance of ammonia, about 20% or more of liquid hydrocarbons boiling up to 200 C.; also about 30% or more of fractions of higher boiling point, and finally up to 20% or more of products of lubricating oil character.

The low-boiling substances can be used,

like benzol or benzine, as motive power for internal-combustion engines. The higher fractions furnish very good Diesel-engine oils, while the fractions of highest boiling points find application as lubricating oil.

N o difficulty is experienced in refining the several fractions by the methods known in the petroleum and coal tar industries; on the contrary it is effected in a very simple manner, with little loss, and in many cases can be omitted entirely.

The process may, of course, also be carried on in a continuous manner, or intermittently, and also by continuously distilling oil' the resulting light products with the gaseous products and unconsumed hydrogen, whilst the last named can be used again for the reaction after the condensable products have been deposited b Y cooling.

(3). 1 kilo of naphthalene and 1 gram of ammonium chloride are heated at about 470 C. for a short time in a suitable pressure vessel, fitted with stirrers and provid ing sutlicient space for hydrogen admitted under a pressure of 100 atmospheres. According to the duration and temperature of the reaction, up to 70% and more of liquid of naphthalene are obtained, including degradation products down to benzol.

(4). In the same manner as in Example 3, 500 grins. of ordinary coal-tar pitch are treated with A grm. of potassium bromide and 1 grm. of iron alum. Up to 70% and over of constituents liquid at the ordinary temperature and boiling, in part, below 200 (1., for the most part between 200 and 360 C., and in smaller amount above 360 C I are formed, the last named constituents being viscous and suitable for use as lubriing oils, whilst the lightest portions are The unaltered naphthav adapted for use as motive power in internalcombustion engines, and the medium fractions in Diesel-engines.

1 kilo of pulverized coal from seams of the most recent possible formation is treated with 1 grm. of potassium iodide, grin. of potassium bromide, l grm. of potas sium chloride and l grm. of ammonium chloride, in the manner described in Example 3. According to the duration and temperature of the reaction, 00% and over of liquid, distillable products are obtained, which can be satisfactorily refined by known methods and are also admirably adapted for use as motor fuel, lubricants, and many other purposes for which the distillates from petroleum or coal tar are employed.

(6). 500 grms. of the crude distillate from brown-coal tar or low-temperature coal tar are treated with grm. of potassium iodide, grin. of ammonium chloride and grin. of ferric chloride, as in Example 3. According to the temperature-which may lie between 200 and 500 pressure and duration of the reaction, products of hen- Zine type are obtained which are admirably suitable for all the general purposes as the various grades of commercial benzine, especially the purest benzines and benzols.

The substances undergoing treatment may be classified as bituminous materials in each instance, employing the definition forth by Abraham in his works such as that given in Asphalt and Allied Substances," 3rd edition, (Van Nostrand), 1929, which is inclusive of various hydrocarbons and mixtures of hydrocarbons from whatever source and in varying degrees of purity, and of solid materials inclusive of lignites, coals, and the like; and in the following claims, the expression bituminous material employed generally as covering the hydrocarbon and allied carbonaceous materials so defined.

hat we claim is 1. The process for hydrogenating and splitting bituminous material, which comprises bringing a l1ydrogcn-lmiring gas, the material and elemental halogen having the catalytic properties of iodine into contact with one another in the presence of a metallic surface having the effect of iron, and effecting a reaction therebetwcen at a pressure above 50 atmospheres and at a temperature above 200 degrees C.

2. A process of preparing lower boiling hydrocarlmns including benzols and benzin s from higher boiling hydrcn-arbons which comprises bringing the higher boiling hydrocarbons into contact with hydro-hearing gas while niairiltaining a pressure above 50 atmospheres and a. temperature above 200 degrees C. in the presence oi a metallic surface having the vii t of iron and a quantity of activ zinger .iaving the catalytic moni. A process of hydrogenating and splitting tarry andpitchy material which comprises introducing a gas bearing free gaseous hydrogen into contact with the material, and effecting a reaction therebetween at a pressure above 50 atmospheres and at a temperature above 200 de rees C. in the presence of material capable of liberating at least one active elemental halogen and in the presence of a metallic surface having the effect of iron.

5. In a process of hydro enating and splitting a bituminous materia the steps of mixing the material in the liquid phase with a small quantity of iodine and with a hydrogen-bearing gas, and then heating the mixture to a temperature of above 200 degrees C. and under a pressure above 50 atmospheres in the presence of a metallic surface having the effect of iron.

process of preparing lower boiling hydrocarbons including benzols and benzines from higher boiling hydrocarbons, which comprises bringing the higher boiling hydrocarbons into contact with hydrogenbearing gas while maintaining a pressure above 50 atmospheres and a temperature above 200 degrees G in the presence of a metallic surface havin the efiect of iron and active iodine, for by rogenating and splitting higher boiling hydrocarbons.

7. The process for hydrogenatingandsplitting bituminous material, which comprises bringing a hydrogen-bearing gas, the material and elemental iodine into contact with one another in the presence of an iron-bearing metallic surface and efiecting a reaction therebetween at a pressure above 50 atmospheres and at a temperature above 200 degrees C.

8. A process of preparing lower boiling hydrocarbons from a bituminous material, which comprises introducing a mixture of the material and a hydrogen-bearing gas into Contact with a metallic surface having the effect of iron, at a temperature of approximately 470 degrees C. while maintaining a pressure above 50 atmospheres in the presence of active halogen having the catalytic property of iodine, tor hydrogenating and aeeaeea 3 splitting higher boiling hydrocarbons in said material.

9. A process of preparing lower boiling hydrocarbons from a sulphur-containing mixture of high boiling bituminous mate- I ing the eilect of iron, at a temperature of approximately 470 degrees C. while maintaining a pressure above 50 atmospheres in the presence of active halogen having the catalytic property of iodine, for hydrogenating and splitting higher boiling hydrocarbons in said material.

10. A process of preparing lower boiling hydrocarbons from a higher boiling bituminous material which comrpises bringing the bituminous material into contact with a hydrogen-bearing gas at a temperature of approximately 470 degrees C. while maintaining a pressure above 50 atmospheres in the presence of elemental iodine and in the presence of an iron-bearing metallic surface.

11. A process of preparing lower boiling hydrocarbons from a mixture of higher boiling bituminous materials, which comprises introducing a mixture of the material and a hydrogen-bearing gas at a temperature of approximately 470 degrees C. while maintaining a pressure of above 50 atmospheres, into contact with a metallic surface having the effect of iron and in the presence oi a metal halide which dissociates with difliculty at the temperature of the reaction and at least one metal salt which will facilitate the dissociation of the metal halide whereby to cause the liberation of active elemental halogen, for hydrogenating and splitting higher boiling hydrocarbons in said material.

12. A process of hydrogenating and splitting bituminous and like coals which comprises introducing a hydrogen-bearing gas into contact with the coal, and efiecting a reaction therebetween at a pressure above 50 atmospheres and at a temperature above 200 degrees C. in the presence of at least one active elemental halogen and in the presence of a metallic surface havingthe effect of lIOll.

13. A process of hydrogenating and splitting bituminous and like coals which comprises introducing a hydrogen-bearing gas into contact with the coal, and efiecting a reaction therebetween at a pressure above 50 atmospheres and at a temperature above 200 degrees C. in the presence of at least one metal-halogen compound and of a metal salt which facilitates the dissociation of the metaLhalogen compound whereby to cause the liberation of elemental halogen for action as a catalyst, and in the presence of a metallic surface having the effect of iron.

1a. A process for hydrogenating and splitting bituminous and like coals which comprises introducing a hydrogen-bearing gas into contact with the coal, and efiecting a reaction therebetween at a pressure above 50 atmospheres and at a temperature above 200 degrees C. in the presence of elemental iodine and an iron-bearing metallic surface.

In testimony whereof we hereunto afiix our signatures.

ADOLF SPILKER. CARL ZERBE. 

